JP2562407B2 - Keratin fiber treatment agent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a keratin fiber treating agent for chemically treating keratin fibers such as hair, wool, and fibers for woolen fabrics, and more specifically, imparting firmness and elasticity to the keratin fibers. Keratin fiber treatment that can be shaped, enhances the effect of shaping keratin fibers by curling, waving, straight perm, etc., and maintains the shape of shaped keratin fibers for a long time and continuously Regarding agents.

[0002]

2. Description of the Related Art Heretofore, there have been reported many keratin fiber treating agents containing a polymer or a conditioning agent for imparting a firmness and elasticity to keratin fibers such as hair, wool, and fibers for woolen fabrics (Japanese Patent Laid-Open Publication No. Sho. 52-7449 and 58-216113). But these are
The effect is exhibited by the treatment agent adsorbing to the surface of the keratin fiber, which causes a feeling of dryness such as a dry feeling accompanying the application of the treatment agent, and the adsorbed treatment agent will fall off if washed, so it is always There was the annoyance that processing had to be performed. In addition, in order to give the original shape of keratin fibers shaping such as curls and waves, a method of shaping with a temporary setting agent such as a blowing agent for hair or a method of semipermanent chemical treatment with a perm solution, etc. Is typical. However, among these methods, the keratin fiber shaped by the temporary setting agent loses its set shape due to an increase in humidity and getting wet with water.
On the other hand, curls and waves produced by perm treatment cause shape loss due to repeated washing, and are not sufficient in the effect of sustaining a desired shape continuously, and in addition, straight curl hair straightening that straightens bent keratin fibers The perm treatment has a problem that the bending of the keratin fibers cannot be satisfactorily corrected.

In order to solve these problems, attempts have been made to penetrate a keratin fiber with a treating agent to continuously modify the fiber itself. For example, a treating agent containing an astringent (special feature: KAISHO 55-108812, 58-1
No. 09405, No. 60-87208), and a treating agent containing naphthalene sulfonic acids (J. Soc. Cosm).
et. Chem. , 36, 87-99 (1985), JP-A-5-43422 and JP-A-5-43425), and a treating agent containing azulene sulfonic acid (JP-A-5-43254)
Nos. 43423 and 5-43426), and a treatment agent for forming a sparingly soluble salt in hair (Japanese Patent Laid-Open No. 1-23320).
No. 8) or a treatment agent containing a metal salt having a valency of 2 or more (JP-A-3-
-275614), but none of the effects were sufficiently satisfactory.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to shape keratin fibers while maintaining their elasticity and elasticity without impairing the supple feel of keratin fibers, and to curl, wave or straight line by chemical treatment. The effect of shaping the shape is enhanced, and the shaped shape for a long time,
It is intended to provide a keratin fiber treating agent which imparts a sustained holding effect.

[0005]

In view of the above situation, the present inventor has conducted diligent research to solve the above-mentioned problems, and as a result, a treatment agent A containing an aromatic compound described below and a polyvalent metal salt were obtained. By sequentially treating the keratin fibers with the treatment agent B contained therein, the elasticity of the fibers can be effectively improved, and the fibers can be shaped while imparting elasticity and elasticity without impairing the supple feel peculiar to the keratin fibers. It has been found that the effect of enhancing the shaping of the chemically treated fiber such as perm and the effect of holding the shaped shape continuously for a long time is excellent, and the present invention has been completed. It was

That is, in the present invention, at least one SO ₄ H or SO ₃ is present in the ring of an aromatic ring compound selected from a benzene ring, a naphthalene ring, an azulene ring, a tetralin ring, an indane ring, a pyrene ring, a fluorescein ring and a coumarin ring. H,
PO ₄ H ₂ , PO ₃ H ₂ , COOH or CH ₂ COOH
The present invention provides a keratin fiber treating agent characterized by comprising a treating agent A containing a substituted aromatic compound and a treating agent B containing a polyvalent metal salt.

In the keratin fiber treating agent of the present invention, the treating agent A contains the above aromatic compound. In the present invention, a naphthalene derivative having a naphthalene ring substituted with the above substituents is preferable. (1):

[0008]

Embedded image Represent differently H, C ₆ H ₅ or a lower alkyl group).

The one represented by

[0010]

Specific examples of the aromatic compound represented by the above chemical formula (1) include 1-naphthylsulfuric acid, 2-naphthylsulfuric acid, 1-naphthol-2-sulfuric acid, 2-naphthol-1-sulfuric acid, 2- Naphthol-3-sulfuric acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1-naphthylphosphoric acid, 2-naphthylphosphoric acid, 1-naphthol-2-phosphoric acid, 2-naphthol-1-phosphoric acid, 2-naphthol-3-
Phosphoric acid, 1-naphthylphosphonic acid, 2-naphthylphosphonic acid, 1-naphthoic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid,
2-hydroxy-3-naphthoic acid, 2-hydroxy-6
-Naphthoic acid, 1-naphthyl acetic acid, 2-naphthyl acetic acid,
2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,
Examples thereof include 4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 8-anilino-1-naphthalenesulfonic acid, and salts thereof.

As the aromatic compound having a ring other than the naphthalene ring, for example, guaiazulene sulfonic acid, tetralin sulfonic acid, indane sulfonic acid,
Oxybenzonesulfonic acid, 1-hydroxypyrene-
3,6,8-Trisulfonic acid, 1,3-dihydroxypyrene-6,8-disulfonic acid, phenylphosphoric acid, fluorescein, carboxyfluorescein, p-phenylbenzoic acid, 7-hydroxycoumarin-3-carboxylic acid, phthalic acid , Isophthalic acid, terephthalic acid, or salts thereof.

Among these, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1-naphthylphosphoric acid, 2
-Naphthylphosphoric acid, 1-naphthoic acid, 2-naphthoic acid, 1
-Naphthyl acetic acid, 2-naphthyl acetic acid, 1-hydroxy-
2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 2-hydroxy-3-
Naphthoic acid, 2,6-naphthalenedicarboxylic acid, 8-anilino-1-naphthalenesulfonic acid, guaizulenesulfonic acid, tetralinsulfonic acid, indansulfonic acid, oxybenzonesulfonic acid, 1-hydroxypyrene-3,6,8-trisulfone Particularly preferred are acids, 1,3-dihydroxypyrene-6,8-disulfonic acid, p-phenylbenzoic acid, 7-hydroxycoumarin-3-carboxylic acid, terephthalic acid and salts thereof.

As these salts, sodium salt, potassium salt, lithium salt, ammonium salt, organic 4
Secondary ammonium salts.

The amount of the above-mentioned aromatic compound having a ring to be added to the treating agent A is 0.1 to 10% by weight (hereinafter, simply referred to as "%").
Is shown), and 0.5 to 5% is particularly preferable.
If it is less than 0.1%, the effect of modifying keratin fibers cannot be sufficiently obtained, and if it exceeds 10%, the effect corresponding to the increased amount is not improved.

Examples of the polyvalent metal salt of the treating agent B containing the polyvalent metal salt of the keratin fiber treating agent of the present invention include magnesium, calcium, barium, iron (II) and iron (II).
I), one or more of hydroxides, fluorides, chlorides, bromides, iodides, nitrates, sulfates, acetates, phosphates, carbonates, etc. of manganese, zinc, nickel, aluminum, lanthanum, etc. Can be mentioned.

Of these polyvalent metal salts, divalent or trivalent inorganic salts or acetates are preferable, and particularly magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate, calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, Ferrous chloride, ferrous nitrate, ferrous sulfate, ferrous acetate, ferric chloride, ferric nitrate, ferric sulfate, ferric acetate, zinc chloride, zinc nitrate, zinc sulfate, acetic acid Zinc, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, alum and the like are preferable.

The amount of polyvalent metal salt to be added to the treating agent B is 0.0.
1 to 10% is preferable, and 0.1 to 5% is particularly preferable.
If it is less than 0.01%, the effect of keratin fiber modification cannot be sufficiently obtained, and if it exceeds 10%, the effect corresponding to the increased amount is not improved.

In the keratin fiber treating agent of the present invention, it is preferable that both treating agent A and treating agent B are added with acid or alkali as a pH adjusting agent to adjust the pH of each treating agent to a specific range. That is, by adjusting the pH to a specific region, the keratin fibers swell sufficiently and the permeation of each treatment agent into the fibers is further promoted. This time,
When the acid is added, the pH of the composition is preferably adjusted to 2 to 5, while when the alkali is added, the pH is preferably adjusted to 8 to 11. If the pH of each treatment agent is less than 2 or more than 11, the keratin fibers may be damaged.

Regarding the swelling of keratin fibers, especially hair by acid or alkali, the research report by Bat et al. {G. R.
Bhat et al. , J. et al. Soc. Cosmet.
Chem. , 32f, 393-405 (1981)}, and according to this, hydrochloric acid is used as the acid and sodium hydroxide is used as the alkali. In the keratin fiber treatment agent of the present invention, an organic acid or phosphoric acid is used as the acid. It is preferable to use ammonia or an organic amine as the alkali.

Specific examples of the pH adjuster used in each treating agent of the present invention include citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, acetic acid, fumaric acid, malic acid, levulinic acid, butyric acid as organic acids. Valeric acid, oxalic acid, maleic acid, mandelic acid, etc .; monoethanolamine, diethanolamine, triethanolamine, as organic amines
Morpholine, N-methylmorpholine, N-ethylmorpholine, morpholine ethanol, piperidine, piperidine ethanol, aminohydroxymethylpropanediol, 2-amino-2-methyl-1-propanol, 2-
Examples thereof include basic amino acids such as amino-2-methyl-1,3-propanediol and arginine.

These acids or alkalis can be used alone or in combination, and the blending amount is preferably 0.3 to 50%, more preferably 0.5 to 30% in each treating agent. When the content of the pH adjuster is less than 0.3%, the swelling effect is small due to the ion exchange ability of the keratin fiber, and even when it exceeds 50%, the effect cannot be increased.

Further, each treating agent of the present invention contains an organic acid sodium salt, potassium salt, ammonium salt or the like,
It is preferred to form a buffer system.

Further, each treating agent of the present invention may be blended with an organic solvent, and particularly in treating agent A, it is preferable to blend a solvent in order to improve the solubility of the aromatic compound.

Specific examples of the solvent include lower alcohols such as ethanol, isopropanol, n-propanol, n-butanol and isobutanol as organic solvents; ethylene glycol, propylene glycol, 1,
3-butanediol, diol such as glycerin, triol; benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-
Aromatic alcohols such as benzyloxyethanol; polyoxyalkylene lower alkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether; N-methylpyrrolidone , N-octylpyrrolidone,
Examples thereof include N-alkylpyrrolidone such as N-laurylpyrrolidone. The amount of these solvents blended in each treatment agent,
0.5-50%, especially 2-30% is preferable.

In each treating agent of the present invention, the balance of the components other than the aromatic compound or polyvalent metal salt and the solvent and the pH adjusting agent is usually water, but it is necessary as long as the effect of the present invention is not impaired. A thickener such as hydroxyethyl cellulose, a surfactant, a fragrance, a pearling agent, a dye, an ultraviolet absorber, an antioxidant, an antiseptic and the like may be blended depending on the case. Further, in order to improve the feel of the keratin fiber, a cationic polymer such as cationized cellulose and a silicone derivative such as dimethylpolysiloxane and amino-modified silicone can be blended.

Further, each treating agent of the present invention includes thioglycolic acid, cysteine, acetyl cysteine, glutathione,
Perming fluid 1 containing a reducing agent such as thioglycolamide
Agent (reduction treatment agent) or two agents (oxidation treatment agent) of perm liquid containing an oxidizing agent such as sodium bromate, potassium bromate, sodium perborate and the like.

As the method of using the keratin fiber treating agent of the present invention, the keratin fiber may be in a dry state or in a wet state after washing. First, the keratin fiber is dipped in the treating agent A or the treating agent A is applied to the keratin fiber. After a certain time,
Preferably, it is left to stand for 5 to 30 minutes, and then the keratin fiber is immersed in the treatment agent B, or the treatment agent B is applied to the keratin fiber,
A method of leaving it in that state, or leaving it for 5 to 30 minutes and then washing it away can be mentioned. In addition, the order of use of each treatment agent in this usage method is changed, and the treatment agent B is followed by the treatment agent A.
Can be used in the same manner as described above. on the other hand,
After dipping or applying each treatment agent, it may be heated to an appropriate temperature, preferably 30 to 60 ° C., when left standing for a certain period of time.
Furthermore, each treating agent of the present invention can be used by being contained in a two-part type perm solution. Specifically, one agent of the perm solution (reduction agent) and the agent of the two perm solution (oxidation) are used. Processing agent B) or processing agent B in 1 perm solution (reduction processing agent) and 2 solutions in perming solution (oxidation processing agent)
It is sufficiently effective to use the treatment agent A contained in the composition.

[0029]

EFFECTS OF THE INVENTION The keratin fiber treating agent of the present invention can shape keratin fibers while continuously imparting elasticity and elasticity without impairing the supple feel of keratin fibers, and keratin by curls, waves, perms, etc. In addition to enhancing the effect of shaping the fiber, it is also excellent in sustaining its shape.

[0030]

EXAMPLES The present invention will now be described by way of examples, which should not be construed as limiting the invention thereto.

Examples 1 and 2 and Comparative Examples 1 to 3 A keratin fiber treating agent having the composition shown in Table 1 was prepared, and the effect of imparting a firmness and elasticity to the keratin fiber was tested by the following method. As the test method, the hair of a Japanese woman who had not been subjected to cosmetic treatment such as cold perm or bleach as the keratin fiber by the time of the test was used.
After soaking at 0 ° C for 30 minutes, washing with ion-exchanged water, and then soaking in treating agent B shown in Table 1 at 40 ° C for 15 minutes,
It is washed with ion-exchanged water, dried, and its tensile elasticity is measured under a relative humidity of 50%. The tensile elasticity of untreated hair measured under the same conditions in advance is set to 1.00,
The tensile elasticity of the treated hair was calculated relatively. The relative values of this tensile elasticity are shown in Table 1.

[0032]

[Table 1]

From the tensile elasticity values shown in Table 1, it was confirmed that the elasticity of keratin fibers was remarkably improved in Examples 1 and 2 using the keratin fiber treating agent of the present invention as compared with Comparative Examples 1 to 3. .

Examples 3 to 7 and Comparative Example 4:

A keratin fiber treating agent having the composition shown in Table 3 was prepared, and a hair bundle of 10 g of hair of a Japanese woman who had not been subjected to cosmetic treatment such as cold perm or bleach as keratin fibers by the time of the test was prepared. After subjecting the bundle to the same treatment as in Example 1, 6 panelists performed sensory evaluation of firmness and firmness. The evaluation criteria are shown in Table 2 and the results are shown in Table 3.

[0036]

[Table 2] Firmness and firmness were remarkably improved over untreated hair: ◎ Firmness and firmness were improved over untreated hair: ○ Firmness and firmness were almost unchanged from untreated hair: ×

[0037]

[Table 3]

From the evaluation of the firmness and firmness in Table 3, the firmness and firmness of Examples 3 to 7 using the keratin fiber treating agent of the present invention was remarkably improved as compared with untreated hair. It was found that the firmness and stiffness of the skin increased even compared to the above.

Examples 8-12:

A keratin fiber treating agent having the composition shown in Table 4 was prepared and the effect of the keratin fiber treating agent of the present invention was tested in the same manner as in Example 3.

[0041]

[Table 4]

In Examples 8 to 12 in which the keratin fiber treating agent of the present invention was used, a remarkable improvement in firmness and firmness was observed.

Examples 13-17:

A keratin fiber treating agent having the composition shown in Table 5 was prepared, and the effect of the keratin fiber treating agent of the present invention was tested in the same manner as in Example 3.

[0045]

[Table 5]

In Examples 13 to 17 in which the keratin fiber treating agent of the present invention was used, a remarkable improvement in firmness and firmness was observed.

Examples 18 to 22: A keratin fiber treating agent having the composition shown in Table 6 was prepared, and the order of use of the treating agent A and the treating agent B of Example 1 was changed to obtain the effect of modifying and improving keratin fibers. For testing, sensory evaluation of firmness and firmness was performed. As a test method, a keratin fiber was made into a hair bundle of 10 g of hair of a Japanese woman who had not been subjected to cosmetic treatment such as cold perm or bleach until the time of the test, and this hair bundle was applied to treatment agent B shown in Table 6 at 40 ° C. After immersion for 15 minutes, it was washed with ion-exchanged water, then immersed in treatment agent A shown in Table 6 for 30 minutes at 40 ° C., then washed with ion-exchanged water and dried to perform a sensory evaluation of firmness and firmness. Table 2 is based on the same evaluation criteria as in Example 3.
Was performed according to The results are shown in Table 6.

[0048]

[Table 6]

In Examples 18 to 22 in which the keratin fiber treating agent of the present invention was used, a remarkable improvement in firmness and firmness was recognized as compared with untreated hair.

Examples 23 to 26, Comparative Example 5:

A keratin fiber treating agent having the composition shown in Table 7 was prepared, and the effect of imparting a firmness and elasticity to the keratin fiber and the effect of continuously shaping the keratin fiber were tested by the following method. Regarding the test method, for the effect of imparting a firmness and stiffness, the hair of a Japanese man who had not been subjected to cosmetic treatment such as cold perm or bleach by the time of the test was used.
After immersing in treatment agent A shown in Table 2 for 30 minutes at 40 ° C., washing with ion-exchanged water, and then treating agent B shown in Table 7 at 40 ° C.
After soaking for 5 minutes, it was washed with ion-exchanged water and dried, and its tensile elasticity was measured under a relative humidity of 50%. The tensile elasticity of untreated hair measured under the same conditions in advance was 1. 00, the tensile elasticity of the treated hair was relatively calculated. After that, this hair is washed 20 times with shampoo and dried again under a relative humidity of 50%, and then the tensile elasticity of the hair is measured, and the elastic elasticity before and after shampoo is compared to give a firmness and firmness to the treatment agent. The effect and its persistence were also tested. On the other hand, regarding the effect of continuously shaping keratin fibers, straight hair of a Japanese woman who had not been subjected to cosmetic treatment such as cold perm or bleach by the time of the test was used, and this hair was made of Teflon with a diameter of 1 cm. After wrapping around the rod of No. 3, treating agent A, treating agent B in the same manner as above.
After removing the hair, the relative humidity is 50
The curl diameter of the hair was measured after drying under%. After that, wash this hair 20 times with shampoo and again with a relative humidity of 50.
%, The curl diameter of the hair was measured, and the curl diameter before and after shampoo was compared to test the shaping effect of the treatment agent and its durability.

[0052]

[Table 7]

Compared to Comparative Example 5, Examples 23 to 26 using the keratin fiber treating agent of the present invention had a higher tensile elasticity immediately after the treatment, and the change in the tensile elasticity was small even after repeated washing. It was confirmed that the keratin fiber treating agent of the present invention imparts firmness and elasticity to the fiber, and its effect is maintained even after repeated washing. Further, regarding the shaping effect of the keratin fiber, Examples 23 to 26 using the keratin fiber treating agent of the present invention have a smaller curl diameter immediately after the treatment as compared with Comparative Example 5, and the keratin fiber is effectively shaped. However, it was confirmed that the effect of shaping the keratin fiber was maintained continuously because the rate of change in curl diameter was small even after repeated washing.

Examples 27 to 30 and Comparative Example 6:

With the composition shown in Table 8, the treatment agent A (perm solution 1
Agent / reduction treatment agent) and treatment agent B (perm solution / oxidation treatment agent) were prepared, and the hair treatment effect of the product of the present invention was tested by the following method. As the test method, the hair of a Japanese woman who had not been subjected to cosmetic treatment such as cold perm or bleach as keratin fiber by the time of the test was used, and the hair was treated with treatment agent A (perm solution 1 agent / reduction) shown in Table 8. 1) at 30 ℃
Soak for 0 minutes, and then treat with treatment agent B (perm solution 2 shown in Table 8).
Agent / oxidizing agent: 30% in 8% sodium bromate aqueous solution)
After dipping at ℃ for 10 minutes and applying a two-component perm treatment,
The hair is washed with ion-exchanged water, dried, and then the relative humidity is 5
Tensile elasticity was measured under 0%, and the tensile elasticity of untreated hair measured in advance under the same conditions was 1.0.
A tensile elasticity of treated hair was calculated as 0. After that, this hair is washed 20 times with shampoo and dried again under a relative humidity of 50%, and then the tensile elasticity of the hair is measured, and the elastic elasticity before and after shampoo is compared to give a firmness and firmness to the treatment agent. The effect and its persistence were also tested. On the other hand, the straight hair of a Japanese woman who has not been subjected to cosmetic treatment such as cold perm or bleach by the time of the test is used, and this hair is wrapped around a Teflon rod with a diameter of 1 cm and then treated in the same manner as above. After treatment with agent A and treatment agent B, remove the hair and remove the relative humidity of 50%.
The curl diameter of the hair was measured after drying under. After that, wash this hair 20 times with shampoo and again 50% relative humidity.
After curling, the curl diameter of the hair was measured, and the curl diameter before and after shampoo was compared to test the shaping effect of the treatment agent and its durability.

[0056]

[Table 8]

Compared with Comparative Example 6, Examples 27 to 30 using the keratin fiber treating agent of the present invention had a higher tensile elasticity immediately after the treatment, and the change in the tensile elasticity was small even after repeated washing. When the invention keratin fiber treating agent was used as a perm solution, it was confirmed that the fiber is imparted with firmness and elasticity, and damage to the fiber due to chemical treatment can be avoided, and that the effect continues even after repeated washing. .
Regarding the shaping effect when the keratin fiber treating agent of the present invention was used as a perm solution, Examples 27 to 30 using the keratin fiber treating agent of the present invention had a smaller curl diameter immediately after treatment than Comparative Example 6. Since the keratin fiber was effectively shaped and the rate of change in the curl diameter after repeated washing was small, it was confirmed that the shaping effect of the keratin fiber was maintained continuously.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naoki Sato 2606-6 Akabane, Kaiga-cho, Haga-gun, Tochigi Prefecture 4-106 Ichikai Shakuya (72) Inventor Takashi Ito 2-9-6-303 Park, Ichikawa-shi, Chiba Prefecture Heim Takizawa

Claims (4)

(57) [Claims] 1. At least one SO ₄ H, SO ₃ H, PO in the ring of an aromatic ring compound selected from a benzene ring, a naphthalene ring, an azulene ring, a tetralin ring, an indane ring, a pyrene ring, a fluorescein ring and a coumarin ring. ₄ H ₂ , P
A keratin fiber treating agent comprising a treating agent A containing an aromatic compound substituted with O ₃ H ₂ , COOH or CH ₂ COOH and a treating agent B containing a polyvalent metal salt. 2. The following general formula (1): Represent differently H, C ₆ H ₅ or a lower alkyl group) and a treating agent A containing a compound represented by the formula [1] and a treating agent B containing a polyvalent metal salt. A characteristic keratin fiber treatment agent. 3. A treatment agent A containing the compound represented by the general formula (1) according to claim 2 and a reducing agent, and a treatment agent B containing a polyvalent metal salt and an oxidizing agent. A keratin fiber treating agent characterized in that 4. A treating agent A containing the compound represented by the general formula (1) according to claim 2 and an oxidizing agent, and a treating agent B containing a polyvalent metal salt and a reducing agent. A keratin fiber treating agent characterized in that